EP0615297B1 - Solid, polyether-based polymeric electrolyte - Google Patents

Solid, polyether-based polymeric electrolyte Download PDF

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Publication number
EP0615297B1
EP0615297B1 EP94200222A EP94200222A EP0615297B1 EP 0615297 B1 EP0615297 B1 EP 0615297B1 EP 94200222 A EP94200222 A EP 94200222A EP 94200222 A EP94200222 A EP 94200222A EP 0615297 B1 EP0615297 B1 EP 0615297B1
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EP
European Patent Office
Prior art keywords
range
polymeric electrolyte
weight
solid
comprised
Prior art date
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Expired - Lifetime
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EP94200222A
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German (de)
English (en)
French (fr)
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EP0615297A1 (en
Inventor
Maria Andrei
Arnaldo Roggero
Massimo Soprani
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Eni Tecnologie SpA
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Eniricerche SpA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes

Definitions

  • the present invention relates to a solid, polyether-based, polymeric electrolyte, to a process for preparing it, and to its use in electrochemical devices.
  • solid polymeric electrolytes also referred to as "ionic conductive polymers” are known, which are constituted by a solution of a ionic compound totally dissolved in a plastic, solid, macromolecular material, which is the polymerization product of monomers containing at least one heteroatom, in particular oxygen.
  • said macromolecular material is polyethylene oxide (PEO), or other polyethers disclosed in U.S. patent 4,471,037; French patents 2,523,769 and 2,568,574; EP-13,037 and EP-13,199.
  • PEO polyethylene oxide
  • the preparation of said electrolytes requires complex, multistep processes which comprise copolymerizing suitable vinyl ethers at temperatures of from -75°C to -80°C, during a time period of 30-60 minutes, dissolving the resulting solid, crosslinked polyvinylether in a suitable solvent, mixing the resulting solution with a solution containing an ionic compound, and finally evaporating off the solvent, in order to obtain a membrane.
  • the purpose of the present invention is of overcoming the above reported drawbacks which affect the prior art.
  • the Applicant has found now, according to the present invention, that the adoption of a particular prepolymer which contains, already included in its molecular structure, the active side ethylene oxide based chains and a large enough number of methacrylic groups, makes it possible the crosslinked polymeric material to be directly obtained by exposure to suitable sources, without using a difunctional comonomer.
  • the present invention relates to a solid, polymeric electrolyte in membrane form, constituted by a solid solution of an ionic compound in a crosslinked polyether, characterized in that said polymeric electrolyte is obtained:
  • the polymerization reaction is carried out in an inert solvent, at a temperature comprised within the approximate range of from -60°C to -30°C, and in the presence of a Friedel-Crafts catalyst, used in an amount comprised within the range of from 0.5 to 3.0 mol per 100 mol of monomers (II) and (III).
  • Suitable catalysts for the desired purpose are etherated boron trifluoride, aluminum trichloride, alkyl aluminum halides and tin tetrachloride.
  • Suitable solvents for the desired purpose are chlorinated solvents, as dichloromethane; and hydrocarbons, as toluene.
  • the catalyst is deactivated by adding an aliphatic alcohol, as methanol.
  • the prepolymer is then recovered by means of usual separation techniques, as a colourless, thick liquid having a weight average molecular weight of the order of 10,000-100,000 as a function of the polymerization temperature.
  • R represents the methyl radical
  • the resulting prepolymer can be characterized by means of such analytical techniques, as NMR and FT-IR.
  • the results from such analyses confirm the absence of the vinylic double bond, and the presence of the methacrylic double bond, which is present at the same level (5-30% by mol), at which it was initially introduced.
  • the vinyl ether (II) can be prepared by reacting ethyl vinyl ether with a polyoxyethylene glycol mono-methyl or -ethyl ether.
  • the monomer (III) can be obtained by reacting diethylene glycol monovinyl ether with methacryloyl chloride in ethyl ether and in the presence of pyridine.
  • the monomers (II) and (III) are obtained with a higher than 99% purity, by using usual separation techniques.
  • the prepolymer (I) is then blended with an ionic compound, in the presence, or less, of a plasticizer and a free radical generating activator, until a homogeneous solution is obtained; the prepolymer is used in amounts comprised within the range of from 20 to 80% by weight, preferably of from 30 to 70% by weight.
  • Suitable ionic compounds for the purposes of the present invention are salts, preferably perchlorates, borates, fluoroborates, thiocyanates, hexafluoroarsenates, trifluoroacetates and trifluoromethanesulfonates of (monovalent or polyvalent) metals, and, in particular, lithium, sodium, potassium, calcium, copper, zinc, magnesium, lead, tin and aluminum.
  • lithium salts and, in particular, lithium perchlorate, and in this case it is used in amounts comprised within the range of from 1 to 30% by weight, preferably in amounts of the order of 3-10% by weight.
  • a plasticizer is present in the blend, in an amount comprised within the range of from 20 to 80% by weight, preferably of from 30 to 70%.
  • Suitable plasticizers for the purposes of the present invention can be selected from oligomers containing ethylene oxide chains or aprotic dipolar solvents with high dielectric constant, low volatility and dissociative properties for lithium salts.
  • oligomers examples include oligoethylene glycol dialkylethers (Diglyme, Tetraglyme) and low-molecular-weight polyethylene glycol dialkylethers (PEGME).
  • oligoethylene glycol dialkylethers Diglyme, Tetraglyme
  • PEGME low-molecular-weight polyethylene glycol dialkylethers
  • solvents examples include propylene carbonate (PC), ethylene carbonate (EC), dimethoxyethane (DME), and mixtures thereof.
  • the free radical generating activator (d), which performs the function of speeding up the crosslinking reaction, thus lowering the exposure times, is present in an amount comprised within the range of from 0.5 to 10% by weight, preferably of from 0.1 to 5% by weight.
  • Suitable free-radical generating activators for the purposes of the present invention are, e.g., benzophenone or benzoin methyl ether.
  • the resulting homogeneous solution is applied onto a solid carrier which can be a plastic material, glass, or a metal sheet; furthermore, the solution can be directly applied onto the surface of a lithium anode or of a composite cathode generally constituted by an oxide, or a sulfide, of a transition metal (V, Mn, Co, Ni, W, Ti), in mixture with an ionically conductive material and an electronic conductor such as carbon black or acetylene black.
  • a solid carrier which can be a plastic material, glass, or a metal sheet
  • the solution can be directly applied onto the surface of a lithium anode or of a composite cathode generally constituted by an oxide, or a sulfide, of a transition metal (V, Mn, Co, Ni, W, Ti), in mixture with an ionically conductive material and an electronic conductor such as carbon black or acetylene black.
  • the so obtained polymeric electrolyte displays a transition temperature comprised within the range of from -100°C to -60°C, as a function of the composition of the blend.
  • the polymeric electrolyte of the present invention is mechanically strong, dimensionally stable, and highly conductive, even at low temperatures.
  • the solid polimeric electrolyte can be used as an electrolytic separator in electrochemical devices, optical displays and sensors.
  • the reaction mixture is heated up to its reflux temperature and is kept under refluxing conditions for 10 hours.
  • the temperature increases from its initial value of 39°C, up to its end value of 42°C.
  • the reaction is then quenched by means of the addition of solid potassium carbonate, and the reaction mixture is submitted to distillation, firstly under atmospheric pressure, in order to remove any ethyl vinyl ether excess and the ethyl alcohol obtained as a reaction byproduct, and then under reduced pressure (2,7 KPa) (20 torr) in order to separate the title vinyl ether from unreacted glycol monomethyl ether.
  • the resulting vinyl ether shows a purity higher than 99% and is obtained in a yield, based on the starting triethylene glycol monomethyl ether, of approximately 80%. Its structure is confirmed by NMR and IR spectroscopy and mass spectrometry.
  • the reaction mixture is heated up to its refluxing temperature (70-80°C) and is kept under refluxing conditions for 10 hours.
  • the reaction product is recovered by extraction with methylene chloride and is separated from the corresponding divinyl ether by distillation. In that way, 40 g (0.3 mol) of diethylene glycol monovinyl ether (yield 40%) is obtained, which is then added to a solution containing 53 ml of pyridine and 40 ml of ethyl ether. To the resulting mixture, kept at room temperature and under a flowing nitrogen stream, 38.3 g (0.32 mol) is slowly added dropwise of methacryloyl chloride, which causes the immediate precipitation of pyridinium hydrochloride. The reaction is carried out until the monovinyl ether is totally disappeared.
  • the difunctional product is recovered from the reaction mixture by HPLC, using silica as the stationary phase and, as eluent, a mixture of hexane and ethyl acetate with a volumetric ratio of 8:1 hexane:ethyl acetate.
  • the resulting product displays a higher purity than 99% and its yield, based on the diethylene glycol monovinyl ether used as the starting product, is of approximately 70%.
  • the reaction is allowed to proceed during 3 hours, with the reaction temperature being kept at -60°C. Then, a methanol excess is added to the reaction mixture, in order to stop the polymerization and remove any hydroxy groups possibly formed during the polymerization reaction.
  • the prepolymer is recovered as a colourless, thick liquid, by extraction with a chlorinated solvent; the yield is quantitative.
  • the prepolymer is characterized by NMR and FT-IR spectroscopy, which confirm the absence of double bonds of vinylic character and the presence of double bonds of methacrylic character, at the same level (10% by mol) as initially charged.
  • the electrolytic polyether-based membranes are prepared according to the following procedure, carried out inside a dry-box, under an argon atmosphere and with a humidity level lower than 5 ppm, using:
  • the resulting blends are cast into constant-thickness films on glass supports and are submitted to U.V. light exposure for 20 seconds. Thus, 5 homogeneous, clear membranes of approximately 100 microns of thickness are obtained.
  • the glass transition temperatures (Tg), as determined by DSC (differential scanning calorimetry), are reported in following Table 2.
  • the membrane conductivity measurement is carried out in a cell provided with two symmetrical electrodes of carbon steel, between which said membrane is compressed, by applying a sinusoidal alternating voltage of 100 mV of amplitude.
  • the line (--•--) relates to the values of conductivity displayed by a membrane (PVE-MMA1) prepared according to the present invention, whereas the line (-- ⁇ --) relates to a membrane prepared according to the prior art (EP-A-638949 corresponding to Italian patent application No. MI92A01008).

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
EP94200222A 1993-02-10 1994-02-08 Solid, polyether-based polymeric electrolyte Expired - Lifetime EP0615297B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI930233A IT1271949B (it) 1993-02-10 1993-02-10 Elettrolita polimerico solido a base poliesterea.
ITMI930233 1993-02-11

Publications (2)

Publication Number Publication Date
EP0615297A1 EP0615297A1 (en) 1994-09-14
EP0615297B1 true EP0615297B1 (en) 1996-10-02

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EP94200222A Expired - Lifetime EP0615297B1 (en) 1993-02-10 1994-02-08 Solid, polyether-based polymeric electrolyte

Country Status (7)

Country Link
US (1) US5417870A (enrdf_load_stackoverflow)
EP (1) EP0615297B1 (enrdf_load_stackoverflow)
AT (1) ATE143748T1 (enrdf_load_stackoverflow)
DE (1) DE69400621T2 (enrdf_load_stackoverflow)
DK (1) DK0615297T3 (enrdf_load_stackoverflow)
ES (1) ES2093483T3 (enrdf_load_stackoverflow)
IT (1) IT1271949B (enrdf_load_stackoverflow)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1276151B1 (it) * 1995-11-17 1997-10-27 Eniricerche Spa Membrana elettrolitica e procedimento per la sua foto-reticolazione su membrana catodica
US6767980B2 (en) * 2002-04-19 2004-07-27 Nippon Shokubai Co., Ltd. Reactive diluent and curable resin composition
US7422826B2 (en) * 2004-04-07 2008-09-09 Greatbatch Ltd. In situ thermal polymerization method for making gel polymer lithium ion rechargeable electrochemical cells
JP4539584B2 (ja) * 2006-02-24 2010-09-08 ソニー株式会社 リチウム／二硫化鉄一次電池
WO2011071101A1 (ja) 2009-12-09 2011-06-16 株式会社日本触媒 電解質材料並びにそれを用いた電池用材料及び二次電池
KR101902281B1 (ko) * 2011-05-19 2018-09-28 에스케이이노베이션 주식회사 수지 조성물용 가소제 및 이를 포함하는 수지 조성물

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908283A (en) * 1986-10-09 1990-03-13 Ube Industries, Ltd. Preparation of ion conductive solid electrolyte
IT1222929B (it) * 1987-10-16 1990-09-12 Enirecherche S P A Elettrolita polimerico solido e generatori elettrochimici che lo contengono
JP2692816B2 (ja) * 1987-11-13 1997-12-17 株式会社きもと 薄型一次電池
IT1231031B (it) * 1989-08-01 1991-11-08 Eniricerche Spa Elettrolita polimerico solido e dispositivi che lo incorporano.
JPH0384807A (ja) * 1989-08-28 1991-04-10 Yuasa Battery Co Ltd 高分子固体電解質
JPH0832754B2 (ja) * 1990-01-06 1996-03-29 株式会社ユアサコーポレーション ポリマー固体電解質
EP0446793B1 (en) * 1990-03-15 1995-08-02 Nippon Oil Co., Ltd. Preparation process of polymeric solid electrolyte
JP2914388B2 (ja) * 1990-04-17 1999-06-28 株式会社ユアサコーポレーション 高分子固体電解質
IT1244483B (it) * 1990-12-21 1994-07-15 Eniricerche Spa Elettrolita polimerico solido a base di poliviniletere reticolato
US5275750A (en) * 1991-07-18 1994-01-04 Matsushita Electric Industrial Co., Ltd. Method of manufacturing a solid polymer electrolyte
JP2851722B2 (ja) * 1991-07-26 1999-01-27 日本石油株式会社 高分子固体電解質およびその製造方法
IT1254941B (it) * 1992-04-28 1995-10-11 Eniricerche Spa Elettrolita polimerico solido a base polieterea

Also Published As

Publication number Publication date
ATE143748T1 (de) 1996-10-15
US5417870A (en) 1995-05-23
IT1271949B (it) 1997-06-10
ITMI930233A0 (it) 1993-02-10
ITMI930233A1 (it) 1994-08-10
DK0615297T3 (enrdf_load_stackoverflow) 1997-03-17
EP0615297A1 (en) 1994-09-14
DE69400621T2 (de) 1997-05-15
ES2093483T3 (es) 1996-12-16
DE69400621D1 (de) 1996-11-07

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